CN1618014B - The use of 1d semiconductor materials as chemical sensing materials, production and operation close to room temperature - Google Patents

The use of 1d semiconductor materials as chemical sensing materials, production and operation close to room temperature Download PDF

Info

Publication number
CN1618014B
CN1618014B CN02827556XA CN02827556A CN1618014B CN 1618014 B CN1618014 B CN 1618014B CN 02827556X A CN02827556X A CN 02827556XA CN 02827556 A CN02827556 A CN 02827556A CN 1618014 B CN1618014 B CN 1618014B
Authority
CN
China
Prior art keywords
sensor
nano particle
analyte
dimention nano
sensor medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN02827556XA
Other languages
Chinese (zh)
Other versions
CN1618014A (en
Inventor
I·贝斯纳德
T·沃斯迈尔
A·亚苏达
M·博格哈德
U·施莱希特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Sony Deutschland GmbH
Original Assignee
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Sony International Europe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Max Planck Gesellschaft zur Foerderung der Wissenschaften eV, Sony International Europe GmbH filed Critical Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Publication of CN1618014A publication Critical patent/CN1618014A/en
Application granted granted Critical
Publication of CN1618014B publication Critical patent/CN1618014B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles

Abstract

The application relates to a chemical sensor device comprising a substrate (1), a sensor medium (3) formed on the substrate, the sensor medium comprising one-dimensional nanoparticles, wherein the one-dimensional nanoparticles essentially consist of a semiconducting AxBy compound, e.g. V2O5 and detection means (2) for detecting a change of a physical property of the sensor medium e.g. conductivity. The porosity of the sensor medium supports a fast access of the analyte to the sensing material and therefore a fast response of the sensor. The selectivity and sensitivity of the sensor can be tailored by doping the one-dimensional nanoscale material with different dopants or by varying the dopant concentration. Sensitivity of the sensor device to an analyte, preferably an amine, can be increased by increasing relative humidity of the sample to at least 5%.

Description

Use the one dimension semiconductor material as the chemical-sensitive material and near producing under the room temperature and operation
The present invention relates to a kind of chemical sensitisation apparatus, relate to the method that obtains this chemical sensitisation apparatus, and with the method for said chemical sensitisation apparatus check and analysis thing.
Carry out many effort in recent years, developed the device that can imitate smell or sense of taste.This class is called as the device of Electronic Nose and electronic tongue usually respectively, can be suitable for the application that haves a wide reach well, such as amusement robot, identification systems, quality control system, environmental monitoring system and medical diagnosis etc.Yet have only the limited Electronic Nose device of number to appear on the market up to now." odorous " sample though these devices can be differentiated or classify must be made the needs that many further application in above-mentioned all application are satisfied in further improvement.These application usually need higher sensitivity, and higher recognition capability is replied faster, better stability and lower power consumption.Because these class characteristics depend on the chemical sensor characteristic that is used for device very doughtily, so strong request improves chemical sensor to satisfy the needs in the application of advanced Electronic Nose and electronic tongue.The summary of the Fundamentals of Sensors in the popular exploitation is taken in " Electronic Nose-principle and application " book 67-116 page or leaf that J.W.Gardner and P.N.Bartlett shown, this book is published by the Oxford University Press, the Oxford, 1999 (" Electronic noses-Principles and applications ").
Some gas sensors are arranged on the market, metal oxide sensor is wherein arranged, the latter is often by the Tagushi sensor.They are made up of the metal oxide of one or more porous forms, and a kind of metal is generally also mixing.They operate so that allow analyte burn on metal oxide surface under the temperature of 100 to 600 ℃ rising, thereby the variation of introducing oxygen concentration causes conductive variation.Metal oxide sensor is generally as the single device that detects poisonous or inflammable gas.They also can be used in the configuration of Electronic Nose, are limited but their application aspect odor discrimination up to now mostly lack enough selectivity.
J.Kong, N.R.Franklin, C.Zhou, M.G.Chapline, S.Peng, K.Cho and K.Dai are at Science, and 2000,287 volume 622-625 pages or leaves have been described a kind of chemical sensor based on Single Walled Carbon Nanotube out of the ordinary (SWNTs).Be exposed to gas molecule such as NO 2Or NH 3In the time, the resistance value of finding semiconductor SWNT in room temperature, be exposed to that only time several seconds promptly changes nearly three orders of magnitude in the analyte molecule.Only time several seconds promptly changes nearly three orders of magnitude in this chemical sensor.This chemical sensor is by by SiO 2The controlled chemistry vapor deposition growth of SWNTs out of the ordinary obtains on the patterned catalyst island on the/Si substrate.The sensor reversibility is by slowly recovering under the room temperature condition or reaching by being heated to high temperature.NO for example 2When air-flow was replaced by pure Ar air-flow, the conduction of SWNT sample was promptly slowly recovered, and be about 12 hours typical release time when room temperature.
Z.W.Pan, Z.R.Dai and Z.L.Wang are at Science, calendar year 2001s 291 volume 1947-1949 page or leaf has been described by at the required commercial metals oxide of high temperature evaporation, come overlength banded nanostructured, the i.e. method of so-called nano belt of the oxide of synthesized semiconductor zinc, tin, indium, cadmium and gallium.He Cheng oxidate nano band is pure, even structure and is monocrystalline like this, and their major parts do not have defective and dislocation.They have rectangular cross section, and its representative width is 30 to 300 nanometers, and width is 5 to 10 to the ratio of thickness, and length then can reach several millimeters.The nano belt that to the mix possible purposes as the nano-scale sensor has been proposed.
People such as V.Bondarenka, S.Grebinskij, S.Mickericius, H.Tsardauskas, Z.Martunas, V.Volkov and G.Zakharova, at Phys.Stat.Sol., 1998, A 169 volume 289-294 pages or leaves have been studied humidity to poly-vanadic acid xerogel and based on the xerogel that gathers vanadic acid, and wherein vanadium is partially by the influence of the electrical properties that molybdenum or titanium replaced.The electricity of film sample is led with exponential function and is increased along with the increase of humidity, thereby makes these films be suitable for the manufacturing of humidity sensor.The film of vanadium-metal-oxygen material is produced by sol-gel technology.Vanadium pentoxide powder and other component are dissolved in the hydrogen peroxide at 273 ° of K.Then solution was heated one/two hour at 353 ° of K in the beaker of opening.The gel that obtains is deposited on the substrate by the screen printing method and in air, dry at 333 ° of K.All compounds that obtain so all have layer structure, and its interlamellar spacing is 11.1 to 11.5 Water cut depends on relative humidity RH in the compound, and increases along with the increase of RH.
People such as S.Capone, R.Rella, P.Siciliano and L.Vasanelli are at Thin Solid Film, and 1999,350 volume 264-268 pages or leaves have been studied bulk material V 2O 5And WO 3The physical property of film and gas sensitive natur.The gas sensitization film of vanadium oxide and tungsten oxide can be prepared into about 200 nano thickness by the spraying plating technology.The sample of supplied gas test is placed on the specimen mounting of heating, and is exposed under the different gas concentration conditions.When high temperature, two kinds of materials all be can be observed the strong index dependence of its electrical conductance to temperature.Can be observed the increase of thin-film electro resistance in the time of in being exposed to NO gas.Based on WO 3Sensor present and compare V 2O 5The Sensitirity va1ue that sensor is higher.In addition, tungsten oxide film also can detect so very NO of low concentration in the inferior ppm scope.V 2O 5Can be used to detect the NO of high concentration, can reach 50-500ppm.
Z.A.Ansari, R.N.Kareka and R.C.Aiyer are at Thin Solid Film, and 1997,305 volume 330-335 pages or leaves have been described the humidity sensor that uses the plane light wave conduit that has various oxide material coating, and the V of other evacuation is wherein arranged 2O 5The effective ion-exchange process of slab guide is installed on the soda-lime glass substrate.The oxide semiconductor film of porous by screen printing on the waveguide surface.Relative humidity (RH) changes to 98% from 3%.Work as V 2O 5Coating length is 3 millimeters, when coating thickness is 25 microns, the response time that presents is 5 seconds, be 30 minutes release time.For V 2O 5Coating is observed 8% hysteresis phenomenon.
People such as R.Rella, P.Siciliano, A.Cricenti, R.Generosi, L.Vanzetti, M.Anderle and C.Coluzza are at Thin Solid Films, 1999,349 volume 254-259 pages or leaves have been studied the physical property and gas one surface interaction of loose vanadium oxide film.The film of vanadium oxide prepares with the active metallikon of r.f..Be the assessment sensitive natur, film its electrical properties of test under the condition that gas with various exists.At Ar-O 2Contain the film of growing under the condition of 15% oxygen in the potpourri and present best sensitive natur, provide maximum replying in the working temperature between 280 and 300 ℃ is thin.
In most of the cases, vanadium pentoxide is and more responsive material, for example WO 3In conjunction with the second kind of unique component that is used for responsive tidal land cloth thing.People such as X.Wang, N.Miura and N.Yamazone are at Sensors and Actuators, and 2000, B66 has reported based on WO in the 74-76 page or leaf 3For detecting NH 3Sensitive material with NO.Prepared the gas sensitive material that is loaded with 1 weight % metal oxide.These materials are for NH 3Be better than pure WO with the susceptibility of NO 3Sensitive thin film.
The vanadium pentoxide film as temperature sensor, is described in Thin Solid Films by Z.S.E1 Mandouh and M.S.Selim, 2000,371 volumes, 259-263 page or leaf.The vanadium pentoxide film prepares with inorganic sol-gel method.The temperature coefficient β of resistance TBe 2%K -1, it shows V 2O 5Can be used as thermal resistance.
WO 98/26871 discloses and has used transition metal oxide, preferably has the made nanotube of vanadium oxide of variable valence state, and this nanotube presents the active and suitable especially active material as catalytic reaction of oxidation-reduction.The structure of the nanotube that synthesizes and obtain of vanadium oxide nanotube has partly been described in its experiment.
WO 01/44796 discloses a kind of nanotube device that comprises a kind of nanotube, preferred carbon nano-tube at least, and its terminal is electrically connected to first and second conduction primitives.This nanotube device can be used as chemistry and biology sensor.For regulating of the sensitivity of this device for various molecular species, can use one or more sensitive agents, by coating or decoration nanotube is modified, thereby give it specific species are had sensitivity in its environment.This nanotube also can form with other material beyond the de-carbon, for example silicon.In experiment, confirmed and can detect various analytes.Experiment is to NO 2And NH 3Gas, thio-alcohol, H 2, CO and avidin (a kind of protein) carry out.Not long-pending metallic particles on sensitive agent has also been described.As gold, platinum or nickel, metal oxide is TiO for example 2Or living species is modified sensitivity.
There is the sensor of some types at room temperature to use, and demonstrates for organic good selectivity.It is the most normal that what run into is conducting polymer chemical resistance device.SAW (surface acoustic wave) and BAW (whole sound wave) device based on polymkeric substance.Yet, the shortcoming that has some to have muting sensitivity in these sensors, for example as conducting polymer chemical resistance device to gas.Based on the device of mechanics transmitter such as cantilever and BAW device than incorporating in the integrated circuit based on the device of electronics transmitter is more difficult.To the sensor based on optical detection, the complicacy of transmitter may be a limiting factor, particularly when considering microminiaturization.About the electrochemical gaging battery, they have only limited purposes in the gas sensor field, but for electronic tongue suitable importance are arranged then.
A general issue when using sensor is a humidity.Found that it has reduced detectability in most sample.First reason relates to such fact, and promptly the distribution of water meeting impact analysis thing in sensor medium perhaps weakens the interaction of analyte and sensor medium.An example is the detection of bouquent.People must be able to detect the trace aromatic in the matrix that comprises big water gaging and alcohol.The variation that second problem is humidity may be counted as false testing result.For example in the occasion of CO detection, relative humidity change 20% should not be interpreted as existing the CO of 50ppm.
A kind of method that reduces humidity problem to greatest extent is the dry analysis thing.People can for example slightly dewater breast before biosensor analysis with sample dehydration itself before analysis is carried out.But shortcoming is a smell variability in dehydration, because volatile matter may be removed or decompose.The head space of sample also can be dried before arriving detecting device.This can pass through, and for example, reaches with a kind of Nafion filter.Water can be by filtering, but some component in the analyte for example alcohols also can be removed partially or all.Water also can be by eliminating with the method for different chemical product in gas chromatography or the similar techniques separating sample.
Have only the limited report of number to claim that humidity is useful, mean sensor demonstrates sensitivity along with the humidity increase increase.Kappler, J.; Tomescu, A.; Barsan, N.; Weimar, U.; Be reported in the SnO of high temperature running at " Thin Solid Films " 2001,391 volume 186-191 pages or leaves Deng the people 2Sensitivity increases along with the increase of humidity gas sensor to CO.Sensor reply (R Air/ R Co) be increased in relative humidity at 50% o'clock from 0 and correspondingly be increased to 30 from 5.Sadaoka, Y.; Sakai, Y.; Murata, people such as Y.N. are at " Sensorsand Actuators " 1993, and B 13-14,420-423 page or leaf report a kind of optical sensor based on calcein-poly-(vinyl cyanide) and present similar behavior in the occasion that detects ammonia.When relative humidity respectively when drying condition is increased to 50%, I/I 0(light intensity ratio) is reduced to 0.83 from 0.95, thereby sensitivity is increased.Other explanation is based on host molecule (tecton DM 189) (Boeker, the P. that is deposited on the mass-sensitive device; Horner, G.; Rosler, S. etc. are at " Sensors and Actuators " 2000, B 70, the 37-42 page or leaf).Compare with the situation in dry air, sensor under the condition that 000ppm water (saturated humidity) exists, is increased to a times of original response value 20 for replying of ammonia (in hertz).
Amine is found and is present in many foods, for example in grape wine, fish, cheese or the meat.Amine can be used as, for example, and the indicator of fish freshness.Amine also can provide some information of relevant human health situation.Like this, just needing the amine sensor aspect food industry and the medical application.These sensors should have high sensitivity for target compound, and preferably can not demonstrate the obvious reduction of sensitivity when moisture exists.Therefore the electronics calculation that comprises such sensor has very big importance.
Some amine gas sensor can be buied from market.For example can buy on the market especially for given amine and the electrochemical gaging pond used for far-ranging amine.Detection limit is 2.5 to 5ppm, and this depends on the kind of amine.The subject matter that exists is aspect size, and it has the size of centimetre-sized.Metal oxide sensor also can be used to detect ammonia, and detection limit is about 25ppm, but their shortcoming is a high power consumption and to the low selectivity of amine.
An object of the present invention is to provide a kind of chemical sensitisation apparatus, it has high selectivity for analyte, and aspect of performance has high sensitivity and high stability, can be near operation under the room temperature condition and have a low power consumption.
For reaching this purpose, the invention provides a kind of chemical sensitisation apparatus, it comprises a kind of substrate and the sensor medium that is formed on the substrate, comprises the 1-dimention nano particle in the sensor medium, wherein this 1-dimention nano particle mainly is by semiconductor A xB yThe type compound is formed, wherein this semiconductor A xB yCompound is to be selected from II-IV-semiconductor, III-V-semiconductor, metal oxide semiconductor (B=O), semiconductor alloy sulfide (B=S), semiconductor alloy phosphide (B=P), metal nitride (B=N), semiconductor alloy selenide (B=Se) and semiconductor alloy telluride (B=Te); And provide method for the physics of detecting sensor medium and/or chemical property variation.
These semiconductor alloy compounds have different selectivity for the different target analyte.Therefore the 1-dimention nano particulate material that is used for the assembly sensor device will be selected according to detected analyte.Semiconductor A xB yThe type compound can be a binary compound, and wherein A and B are respectively single-elements.Example has SnO 2And MgO.Further, they also can be ternary or quaternary compound, for example GaAs/P.Preferred x＞0 and y＞0.
A preferably is selected from least a element among V, Fe, In, Sb, Pb, Mn, Cd, Mo, W, Cr, Ag, Ru and the Re.B preferably is selected from least a element among O, S and the Se.
Semiconductor A xB yMetal in the type compound (A in the compound) can be single oxidation state exist.Preferably at single semiconductor A xB yHave at least a kind of element (A or B) to exist in the type compound with different oxidation state.Most preferably elements A exists with different oxidation state.Ratio between two kinds of oxidation state is preferably in 0.001 to 0.1 scope.When using for example V 2O 5During as the 1-dimention nano particulate material, vanadium can V 4+And V 5+State exist.At V 2O 5Occasion under, mixed valence is because the defective in the structure produces.
Like this, just not obvious from the valence mumber of formula mixing.Another example of mixed valence compound is Fe 3O 4, wherein in the stoichiometry index indication material Fe is arranged IIAnd Fe III, and the ratio of Fe ion equals 0.5 in oxidation state II/III.Form for example oxide and sulfide, wherein the element further example that can be in different oxidation state has cobalt, chromium, lead, titanium, rhenium and molybdenum, the further example that the oxidation state that wherein element can be different under the occasion of oxide exists has aluminium, gallium, germanium or indium.In a kind of given material, can run into two kinds of different oxidation state (mixed valence).Sn is as Sn IIBe present among the SnO, as Sn IVBe present in SnO 2In, as Sn IIAnd Sn IVBe present in Sn together 3O 4In.Similarly, Sb is found with Sb IIAnd Sb IVBe present in the oxide, and (III and V) is present in Sb 2O 5XH 2Among the O.Chromium can II, III, the oxidation state of IV and VI forms oxide, and (II and III) is present in Cr 3O 4In.Similarly behavior also is that known [II, III, IV, VII and (II and III) are present in Mn to manganese 3O 4In], (I and III are at Ag to also have silver 2O 3In).
Mixed valence also can be introduced by defective, for example by adulterant or a kind of impurity.Thereby make semiconductor A by providing the element that is in different oxidation state can control charge carrier concentration xB yThe electrical conductance of type compound is strengthened in room temperature.By creating possible response location, for example by introducing defective, the sensitivity of sensor can be enhanced.
In sensor device of the present invention, be used as the 1-dimention nano particle of sensitive media, vertically have than perpendicular to the much bigger extension of direction longitudinally.Usually nano particle is a micron order in dimension longitudinally, and is nanoscale in the dimension of both direction perpendicular to it.Preferred 1-dimention nano particle has the length less than 100 microns, is more preferably less than 15 microns, and most preferably between 100 nanometers and 15 microns, and its xsect is less than 100,000 nanometers 2, preferably less than 5000 nanometers 2, especially preferably less than 50 nanometers+.The length of 1-dimention nano particle can be controlled by the reaction time in the synthesizing one-dimensional nano particle process easily.Therefore the 1-dimention nano particle has the shape of fiber, is not easy self assembly and forms closelypacked arranging, as for example those have spherical nano particle.Like this, the vacancy in sensor medium can increase, and allows analyte that better chance near the one dimension sensitive material is arranged.The sensor medium of sensor device of the present invention provides analyte to be easy to approaching very high surface area, and this makes sensor medium have high sensitivity, and sensor device is had fast reply.
The 1-dimention nano particle is present in the sensor medium with particle out of the ordinary.As long as by physics interact and the 1-dimention nano particle deposition on substrate surface, stabilization sensor medium fully.For increasing the mechanical stability of sensor medium, the 1-dimention nano particle can pass through, and for example, interconnecting of difunctional ligand perhaps is embedded in it in the matrix.
Be used for the 1-dimention nano particle of sensor device of the present invention, made by semiconductor material, the latter is basically by semiconductor A xB yThe composition of type compound.Depend on semiconductor A xB yThe character of component A and B in the type compound, this 1-dimention nano particle are for given analyte, and the sensor comparison with based on carbon-SWNT has different selectivity, describes in above-mentioned carbon-people's such as J.Kong that the SWWT sensor is quoted as proof in front the article.Obtain the method that picture is used for this 1-dimention nano particle of sensor device of the present invention, be established well.This 1-dimention nano particle can easily modified aspect their composition, for example by adding adulterant, so this sensor device can be made at target analytes.
Chemical sensitisation apparatus of the present invention can be operated under the condition near room temperature, thereby have low power consumption, because general heating sensor medium again.This also makes sensor of the present invention operate easily.Common this sensor is to be lower than operation below 100 ℃, preferably to be lower than 50 ℃, particularly preferably in ambient operation.This sensor can low cost be produced, thereby also can be by the microminiaturized integrated circuit some that forms.
The 1-dimention nano particle can be hollow or enrich, and can have the form of nanotube for example or nano wire.The preferred 1-dimention nano particle that enriches.Further, this 1-dimention nano particle can have various shape of cross sections, and the xsect of circle (annular) or rectangle for example can be arranged.Like this, this 1-dimention nano particle can have the form of nano wire or nano belt.Nano belt is particularly preferred sensitive material.This sensor medium also can comprise many bundle 1-dimention nano particles.
Synthesizing of the 1-dimention nano particle that II-IV-semiconductor or III-V-semiconductor form, be described in Adr.Mat. by for example X.Duan and C.M.Lieber, 2000,12,298 to 301 pages.The III-V family material that can be used for binary in the sensor of the present invention has for example GaAs, Gap, InAs and InP.Ternary III-V family material has GaAS/P or InAs/P, and the example of binary II-IV compounds of group has ZnS, ZnSe, CdS and CdSe.The 1-dimention nano particle is come out with in enormous quantities, prepared in high purity by above-mentioned semiconductor material.Nano wire, for example, the catalytic growth method (LCG) that available laser helps prepares.
The nano particle of metal oxide semiconductor, the method for describing in the material that people such as available Z.W.Pan quoted as proof in front preparation.Can be used as semiconductor that preparation is used for the 1-dimention nano particle source of sensor device of the present invention and can belong to oxide and have, for example Ga 2O 3, SnO 2, In 2O 3, PbO 2, MgO, Fe 2O 3, W 18O 49And GeO 2By the 1-dimention nano particle that semiconductor alloy sulfide is formed, can be from MoS 2, NbS 2, TiS 2, WS 2, W 0.7Mo 0.2C 0.1S 2Preparation.Suitable preparation MoS 2, WS 2And the method for BN nanotube is described in Adv.Mat. by for example people such as M.M.Nath, A.Govindaraj and C.N.R.RaG, 2001,13 volume 283-286 pages or leaves.
Patzke, G.R.; Krumeich, F.; Nesper, people such as R. be at Angen.Chem.Internat.Edit.2002, and 41 volumes, 2446-2461 page or leaf have been reported oxide (Fe for example 2O 3, Fe 3O 4, In 2O 3, Sb 2O 3, SnO 2, TiO 2And SiO 2) nanotube and the method that forms of nanometer rods.Si 3N 4Nano particle synthetic by Han, W.; Fan, S.; Li, Q; Hu, people such as Y are described in Science 1997,277 volume 1287-1289 pages or leaves; And Remskar, M.; Mrzel, A.; Skraba, Z.; Jesih, A.; Ceh, M.; Demsar, J.; Stadelmann, P.; Levy, F.; Mihailovic, D.; At Science, 2001,292 volume 479-481 pages or leaves have been described the synthetic of the 1-dimention nano particle made from GaSe Deng the people.
The 1-dimention nano particle can be used porous templates, and for example the porous polycarbonate film prepares (Kovtyukhova, N.I. by the compound that haves a wide reach; Mallouk, T.E.Chem.Eur.J.2002,8,4355-4363; Mbindyo, J.K.N.; Mallouk, T.E.; Mattzela, I.B.; Kratochvilova, I.; Ravazi, B.; Jackson, T.N.; Mayer, T.S.J.Am.Chem.Soc.2002,124 volume 4020-4026 pages or leaves), perhaps use the one dimension template.The example of one dimension template has carbon nano-tube or organic fiber.Template can be removed by suitable technology, for example by thermal decomposition or etch, thereby only stays required 1-dimention nano particle.Detailed knowledge for the 1-dimention nano particle growth is given in, for example, and Caraso, R.A.; Schattka, J.H.; Graeiner, people such as A., Adv.Mat.2001,13 volumes, 1577-1579 page or leaf.
Above-mentioned material can respective pure form use the use of also can interosculating.For example, can use by pure V 2O 5The 1-dimention nano particle of making.One dimension V 2O 5Physical property can be by further toward one dimension V 2O 5Add for example WO of material in the material 3Modify.Further different 1-dimention nano particles by different semiconductor material manufacturings.Can be applied in the single sensor information of chemical sensor of the present invention.So this sensor medium comprises, for example by first kind of semiconductor A xB yFirst kind of 1-dimention nano particle that the type compound is made, and by second kind of semiconductor A xB ySecond kind of 1-dimention nano particle that the type compound is made.
Best this semiconductor 1-dimention nano particle is made by vanadium oxide material.Vanadium pentoxide 1-dimention nano particle obtains with the virgin material form in large quantities by wet chemistry methods easily.They can nanotube and nanofiber or two kinds of forms acquisitions of nano belt.The vanadium pentoxide nanofiber demonstrates suitable electric conductivity and can be used as the coating thing of chemical resistance apparatus.
The vanadium pentoxide nanotube can synthesize by template with a kind of amine.This method, for example, by H.J.Mukr, F.Krumeich, U.P.Chonholzer, F.Bieri, M.Niederberger, people such as L.J.Gaukler and R.Nesper are described in Adv.Mat., 2000,12 volume 231-234 pages or leaves.The effect of amine is a cambium layer, and the latter rolls volume and forms the pipe of many walls.Amine can be easily with the neutral amine exchange or by its kation of proton exchange later on.If do not use template in synthetic, vanadium pentoxide may form the band shape with rectangular cross section.The vanadium pentoxide nano belt is the good solid of assembling with certain dimension.They form the about 1-5 nanometer of thickness, about 10 nanometers of width, the length ribbon greater than 500 nanometers.They are n-N-type semiconductor Ns that polymerization on acid-exchange resin (partially) ammonium vanadate produces.Synthesizing of this vanadium pentoxide nano belt by O.Pelletier, P.Oavidson, C.Bourgauk, C.Coulon, people such as S.Regnault and J.Livage are described in Langmuir, 2000,16 volume 5295-5303 pages or leaves.
This 1-dimention nano particle can use with unadulterated form as the form that it is synthesized.In order to modify and of the present invention Selectivity of Sensor and the sensitivity of metering needle to target analytes, this 1-dimention nano particle can mix with a kind of adulterant.The sensor that has suitable adulterant is super-sensitive and can be lower than check and analysis thing under the such concentration level of 1ppm.
Can use ion as adulterant, they can be merged in the structure of 1-dimention nano particle, or are fixed on their surface.By exchanging proton at the 1-dimention nano particle surface.This may accomplish.Under the occasion of vanadium oxide, the most of vanadium atom that is included in the one dimension vanadium oxide material in the sensor medium of sensor of the present invention has (V) valency, and 10% vanadium atom is in (IV) valency state but have nearly.Be the disappearance of compensation charge, the surface of fiber is promptly by protonated.These protons can easily be exchanged, and introduce adulterant simultaneously in film.Have only some in these protons be doped exchange.T.oradin, D.Israel, J.C.Badot and W.Battier be at Mat.Res., Bull, and 2000,35 volumes, 1907-1913 page or leaf described nearly that 15% above-mentioned proton can be exchanged by most of kation.Only contain when using+during the vanadium oxide of V oxidation state,, on the surface of 1-dimention nano particle, may form hydroxyl by the part hydrolysis of vanadium oxide in water.This class hydroxyl is acid, its proton can by kation for example Ag+ exchange.Can reach higher doped level by oxidized metal in solution.The vanadium pentoxide of silver-doped is by F.Coustier, and S.Passerini and W.H.Smyrl are described in " Solid state Ionics ", 1997,100 volume 247-258 pages or leaves.Inserting heavy ion can be by little kation institute catalysis.The purpose of small cation is the layer structure of material of bursting apart, thereby the exchange of macrocation is achieved.
This 1-dimention nano particle also can add neutral molecule by the interlayer embedding at the 1-dimention nano particle and mix.Mean like this between the different layers of 1-dimention nano particle, make the weakening of interaction force owing to structure expands.The interaction of such central element between vanadium pentoxide xerogel different layers by, for example, described in the document that people such as T.Coradin quote as proof in front, also by H.P.Oliveira, people such as C.F.O.Graeff and J.M.Rosolen is described in Mat.Res.Bull, 1999 34 volume 1891-1903 pages or leaves.Also can be fixed on molecule or particle on the surface of 1-dimention nano particle.
The adulterant of sensor of can be used to mix is some ions, as the Au (III) of source family chlorauride or acetic acid gold, also can use the Au (I) or the Ag (I) that come from acetate or nitrate.Can also immerse the 1-dimention nano particle and contain with in the solution of solid forms as the metal of adulterant.Metal is oxidized and incorporate in the 1-dimention nano particle then.A kind of like this metallic ion is incorporated into method quilt in the vanadium pentoxide xerogel, for example, F.Coustier, G.Jarero, people such as P.Passerini and W.H.Smyrl are described in " Journal of Power Source ", 1999 years, 83 volume 9-14 pages or leaves, they use the V of copper doped 2O 5Xerogel is as the composition of cathode material in the coin battery device.
Further, this 1-dimention nano particle can mix with organic molecule.There are various organic molecules can be used as adulterant.This class organic molecule can be to contain one or more heteroatomic hydro carbons, and these heteroatomss can form the group of polarity.Suitable heteroatoms has for example oxygen, nitrogen, phosphorus or sulphur.Suitable organic compound for example has, aromatic series or aliphatic thio-alcohol, carboxylic acids, amine, phosphine class, phosphine oxide class, pyridine and pyridine derivate, thiophene and thiophene derivant, pyrroles and azole derivatives.These organic molecules are attracted to the surface of 1-dimention nano particle or are embedded in the interlayer of 1-dimention nano particle, thus the physics and the chemical characteristic of having modified the 1-dimention nano particle.For example, T.Kuwahara, people such as H.Tagaya and J.Kodokawa are at " Inorganic Chemistry Communioations ", and calendar year 2001 the 4th rolls up to have reported on the 63-65 page or leaf organic dyestuff is embedded stratiform V 2O 5Host lattice in.Pyridine derivate is embedded V 2O 5By Y.Shan, R.H.Huang and S.D.Huang are described in " Angewandte Chemie " in the xerogel, Interational Edition, 1999 the 38th volume 1751-1754 pages or leaves.Further, this kind one-dimensional nano particle can also mix with conducting polymer.This class inorganic-organic hybridization thing microstructure can be from J.H.Harreld, B.Ounn and L.F.Nazar are at " International Journal of Inorganic Materials ", volume 135-146 page or leaf recognized that wherein the author had prepared vanadium oxide-polypyrrole hybrid aerogel in 1999 the 1st.Further also can incorporate big organic cation in the structure of 1-dimention nano particle into.By, M.Inagaki for example, people such as T.Nakamura and A.Shimizu are described in J.Mater.Res. to this class material, 1998 the 13rd volume 896-900 pages or leaves.The author has prepared the embedding compound by ammonium cation and vanadium oxide xerogel.As some of the present invention, organic molecule incorporate the sensitivity that has increased organic vapor into.Can suppose that organic molecule promoted the interaction with the picked-up of steam and steam.
Ion complex also can be used as adulterant and come the doped one-dimensional nano particle.A kind of ion complex that can be used as adulterant of the present invention be for example the inferior gold of thioglucose or with the metal complex of big organic molecule, as phthalocyanine or porphyrin.People such as the H.P.Oliveira that quotes as proof have previously described porphyrin-copper complex have been embedded V 2O 5Method in the xerogel.
According to embodiment preferred of the present invention, also contain second kind of nano-particle material in the sensor medium in the chemical sensitisation apparatus in addition, the latter preferably has the shape of almost spherical.Incorporating the second kind of nano particle that is different from the 1-dimention nano particle in sensor medium into allows sensor selectivity and transducer sensitivity are modified.Metal nanoparticle can be by forming to predetermined fixed evaporation of metal on the 1-dimention nano particle on the substrate.Further the metal nanoparticle with organic shell stabilization can prepare by for example wet chemistry methods.A kind of method for preparing this type nano granular by, for example, M.Brust, J.Fink, D.Bethell, people such as D.J.Schiffrin and C.Kiely are described in J.Chem.Soc., Chem.Commun., nineteen ninety-five 1655-1656 page or leaf.This technology can be applied to far-ranging metal nanoparticle.Example has Fe, Au, Ag, Pt, Pd and some bielement nano particle such as Fe/Pt.The nano particle of this class stabilization is dissolvable in water in the ordinary organic solvents.These nano particles will immerse in the solution of corresponding second kind of nano particle, and be fixed on the 1-dimention nano particle by simply the substrate that is being coated with the 1-dimention nano particle in advance.Chemical coupling between 1-dimention nano particle and second kind of nano particle is possible by difunctional or the organic connection compound of polyfunctional group.At last, some metal ion complexs are in case in solution, just can produce the metallic particles that can be fixed by last art dip operation.This metalloid complex compound has silver acetate or AuS (CH 3) 2Cl.
Based on the chemical sensor of vanadium pentoxide nano belt, also be responsive to hydrogen.By the vanadium pentoxide nano belt of mixing with metal, for example gold, its sensitivity promptly is enhanced.Can use nano particle through organic shell stabilityization, or by the evaporation thin metal layer, or with the slaine that can be converted into nano particle, in the doping process, mix.
According to embodiment preferred, second kind of nano particle is made up of semiconductor material.Can use for example II-IV and III-V semiconductor as semiconductor material, as Cd 3P 2Or PbS 2
For given analyte, the sensitivity of sensor is influenced by the assorted agent of bid.For detecting CO, for example have for the suitable adulterant of vanadium pentoxide nano belt:
-come the platinum of spontaneous evaporation thin layer;
-FePC (III);
-by the evaporation thin layer or with Aus (CH 3) 2The metallic gold that Cl mixes and obtains with highly doped level.
Chemical sensitisation apparatus of the present invention can detect a kind of analyte with each censure physics and/or chemical property.In first group, the variation of electrical properties is detected.For example, electrical conductance or changes in capacitance that can the survey sensor medium.Like this, the chemical sensitisation apparatus can work as chemical resistance device or chemical capacitor.Sensor medium also can be used to form the device of chemical diode or a kind of multiterminal in a kind of structure, such as chemical transistor (chemistry-FET) for example.Chemosensitive transistorized example comprises the semiconductor oligomer based on polythiophene, be described in the document recently (referring to B.Crone, A.Dodabalapur, A.Gelperin, L.Torsi, H.E.Katz, A.J.Loringer, people such as Z.Bao, Appl.Phys.Lett., calendar year 2001 the 78th is rolled up the 2229-2231 page or leaf).This chemical sensitisation apparatus also can be used as the mass-sensitive sensor.The sensitive thin film that comprises the 1-dimention nano particle promptly is used as the coating thing of doing on the piezoelectric, installs to form chemosensitive surface acoustic wave (SAW), or quartz crystal microbalance (QCM) or a kind of cantilever, or the combination in any of this class sensor type.
According to another embodiment, this chemical sensitisation apparatus is used as a kind of optical sensor.So it is measured that sensor signal can be used as the variation of reflectance, fluorescence, absorption or scattering.In this case, analyte molecule is adhered to the variation that can cause optical property (ultraviolet/visible and/or infrared light) on the sensor material.For example, when analyte molecule was adsorbed on the semiconductor 1-dimention nano particle, its luminosity promptly may change.This variation is because due to the immediate environment of the electronic state of 1-dimention nano particle and/or 1-dimention nano particle changes.Further, this 1-dimention nano particle may with suitable chemicals, for example dyestuff combines, thereby introduces change of optical property when interacting with a kind of analyte.
Also may utilize sensor medium to be used for fiber optics (for example auroral poles, interferometer) as chemosensitive coating thing.This chemical sensitisation apparatus also can utilize heat or variation of temperature, thereby is used as thermistor, or other thermoelectric device.
Preferably this chemical sensitisation apparatus is set up into the chemical resistance device, and sensor medium wherein is by the addressing of a pair of contact electrode institute.
This sensor medium can be deposited on the interdigital electrode that for example is made of gold by form of film, and gold then for example is deposited on the inert substrate by lithographic techniques, and perhaps two electrodes can be deposited over the top of film.The structure that also has other.An electrode can be placed on below the colorimetric sensor films, and another resistance can be deposited on the top of colorimetric sensor films.By the analyte sorption to the 1-dimention nano particle, the electrical properties of sensor is affected, and causes the variation of colorimetric sensor films electric conductivity.
A well heater can be provided on sensor medium, control temperature and when needed the heating sensor medium make its regeneration.The purpose of well heater also can be adjustment in required scope.The evaluation that can carry out analyte when finishing a collection of signal analysis is with quantitative.Temperature sensor also has the advantage of monitoring true temperature.
When chemical sensor was self-contained within the IC device, inert substrate can be used for example Si/SiO 2Make.Further preferred substrate is made with glass and/or pottery.
Can be arranged into sensor array with some chemical sensors, preferably the medium of these sensors has different compositions and/or operates under different temperatures.Different analytes are selected sensor and the requirement of sensitivity in order to adapt to, and are not only the character of adulterant, and it all is important also having doped level.Like this, be the purpose as Electronic Nose, the sensor array with dopant concentration gradient can be used as array.
The size that the 1-dimention nano particle is very little can make device microminiaturized at an easy rate.So chemical sensor of the present invention can be by microminiaturization, and, for example, be applied in the sensor array of IC device.
Be used for the 1-dimention nano particle of chemical sensitisation apparatus of the present invention, have quite high electric conductivity.When vanadium pentoxide is used as this 1-dimention nano particle especially like this.Vanadium oxide comprise be in+the IV valency and+vanadium of V valency state, therefore just can provide good electrical conductivity in room temperature.
The sensitization of sensor device of the present invention may be based on interactions dissimilar between analyte and the sensitive material.Analyte can be attracted on the surface of 1-dimention nano particle or be embedded in the structure of sensitive material.Depend on the length of one dimension sodium rice particle, the sensor device that comprises single 1-dimention nano particle also may be preferred.In this case, two spaces between the electrode in preferably single 1-dimention nano particle bridging.Single 1-dimention nano particle has been enough for obtaining sensor medium, but also can be arranged with parallel arranging more or less by some nano particles.Than the 1-dimention nano particle of void size smaller szie between the electrode pair can be arranged form network-like.So the 1-dimention nano particle forms intersection thereon, contiguous nano particle contacts each other, thereby provides pathway between electrode.Via the electrical transmission of vanadium pentoxide nano wire out of the ordinary by J.Muster, G.T.Kim, V.Krstic, J.G.Park, Y.W.Park, people such as S.Roth and M.Burghard are described in Adv.Mater., 2000 the 12nd volume 420-424 pages or leaves.
Astoundingly, sensor device of the present invention increases under higher relative humidity condition for a kind of sensitivity of analyte.Like this, this sensor preferably draws with humidity or the moisture measurement unit combines.Under first kind of situation, controlled humidity guarantees that sensor has reproducible replying.Under second kind of situation, analyte concentration can be used, and for example, the correction data group also considers that the humidity value that records decides.
Above-mentioned chemical sensitisation apparatus can easily be assembled.Like this, the invention further relates to the method that forms above-mentioned chemical sensitisation apparatus, it may further comprise the steps:
A) provide substrate with substrate surface;
B) provide basically by semiconductor A xB yThe 1-dimention nano particle that the type compound is formed, wherein the definition of A, B, x, y is identical with the front;
C) thus obtain sensor medium with 1-dimention nano particle coated substrate surface;
D) provide the physics of detecting sensor medium and/or the detection method that chemical property changes.
The 1-dimention nano particle can prepare with known method.Obtain one dimension vanadium pentoxide material method summary can referring to, for example, J.Livage, " Coordination ChemistryReview ", 178-180 page or leaf in 1998 and 999-1018 page or leaf.The characteristic of chemical sensor of the present invention can be synthesized condition to be influenced.In the process of preparation 1-dimention nano particle, add surfactant and can introduce high porosity, this is by s.Mage, M.verelst, P.Lecante, E.Perez, people such as F.Ansart and J.M.Savariault are in 1998 the 238th volumes of Journal of non-Crystalline Solids 37-44 page or leaf, and the gel that relevant vanadium alkoxy is derived is specified.When surfactant existed, porosity can be up to 75%, and when not having surfactant, then only was 5%.Under the device situation that has than greater number fiber, increase porosity with the rate of diffusion of enhancing analyte molecule in sensor medium, thereby improve response time and sensitivity, obviously be useful.
The 1-dimention nano particle can be by rotary coating, drip be coated with, dip-coating, brushing technology, ink-jet printing technology or any other technology be deposited on the substrate.
This 1-dimention nano particle can be located aligning in deposition process, for example, and can two chemical resistance devices of bridge joint electrode.When only forming sensor medium and allowing manufacturing process to have high reappearance with a little nano particle, the location calibration of 1-dimention nano particle is preferred.The location of 1-dimention nano particle calibration can pass through MIMIC (in kapillary miniature molded) technology, the described method of people such as the H.J.Muhr that promptly quotes as proof previously, perhaps the usefulness method that applies magnetic field is reached.The liquid ciystal suspension of vanadium pentoxide ribbon is passed through magnetic field orientating by X.Commeinhes, P.Davidson, and people such as C.Bourgaux and L.Livaqe are described in Adv.Mat., 1997, the 9 volume 300-903 pages or leaves.
This sensor device has the sensitivity of increase to the detection of amine under the high humidity levels condition.Further, this sensor device is for other analyte, and humidity only shows slight influence to replying.For obtaining high reproducible result and/or for detecting, for example, very the amine of low concentration level is preferably providing humidity conditioner and/or moisture measurement unit with the sensor medium place of being closely related.
Above-mentioned chemical sensitisation apparatus has high selectivity and high sensitivity to analyte, and has response time and release time fast.Like this, a method that further theme is an analyte in a kind of test samples of the present invention, above-mentioned chemical sensitisation apparatus and the detection method that contains sensor medium wherein is provided, sample is applied on the sensor medium, then the variation of the physics of determination sensor medium and/or chemical property.
Above-mentioned chemical sensitisation apparatus all is responsive to different gas and organic vapor.They also can be used to detect the analyte in the solution.The major advantage of chemical sensitisation apparatus of the present invention is, it can be near operation under the room temperature condition and its high sensitivity.
When using the vanadium pentoxide nanofiber as the 1-dimention nano particle, this chemical sensitisation apparatus is to for example CO, H 2, NH 3Be responsive, to SO x, O 2Or NO xAlso be responsive.This sensor is extremely sensitive for the organic molecule of ammonia and polarity such as amine or thio-alcohol, may detect this class material of the concentration that is lower than 0.5ppm.By changing adulterant, might create the sensor that can cover the whole concentration range of given gas with identical raw material.Sensitivity for amine allows sensor device of the present invention is applied to, and for example, in the food industry, monitors the processing of food.
Based on V 2O 5Sensor generally very fast to replying of gas.Response time can be along with interested gases/vapors and adulterant and is changed.Even may reply slowlyer, also can obtain big signal after 1 minute, this application for the Electronic Nose aspect is enough.
The reversibility of signal is fine, and in most of the cases, when in ambient operation, 90% of signal promptly recovers in 2-3 minute.
Use sensor device of the present invention, the sensitivity meeting is accompanied by the increase of relative humidity and increases, and condition is the analyte amine.Detection can be carried out in broad humidity range.Preferred relative humidity is higher than 5%, and most preferably relative humidity is higher than 20%, to guarantee to have sufficient signal intensity.
For obtaining reproducible result from sensor device, in the process of the change in physical of determination sensor medium, preferably keep the relative humidity level of analyte constant in constant level.
Humidity has different influences to different analyte sensitivity, and this can be utilized to the discriminatory analysis thing.Replying when this programme element is a kind of analyte of comparison humidifying and dry this analyte.For example, humidity is for using V 2O 5The influence of sensitivity is very little when analyzing propyl alcohol.Therefore in such structure, wet, doing two kinds, to reply be similar.Yet, at V 2O 5A kind of amine is made when replying, be far longer than signal when being placed between the sensor of sample to a kind of drying agent by the signal of the analyte of humidifying.Like this, during with such scheme, the difference of third alkohol and amine is just very directly perceived.
Sensor device of the present invention is very sensitive to the mensuration of amine.The inventor can confirm, under high humidity, might detect the low amine that reaches 30ppb concentration.When food ferments, often can meet biogenetic amine.For example, in the decomposable process of fish, can produce trimethylamine or ammonia.Like this, volatile amine just can be used as the indicator of fish freshness.Grape wine also contains volatility amine.Their influence is limited to ruins taste vinous, but when more serious, the health that also may jeopardize the consumer.Can easily finish detection with method of the present invention to these volatility amines.Further, also can detect the amine in the body fluid, for example sweat, urine, breathing breath or blood all are possible; Like this, the present invention's method of detecting a kind of analyte, preferred a kind of amine just may be applied in the medical diagnosis.For example, dimethylamine in patient's breath and trimethylamine are the indications of uremia (kidney failure).Breast cancer also can obtain diagnosis by the specific distribution of volatility amine in the urine.In addition, ammonia often is used in the chemical industry, and detection method of the present invention can be used to detect the leakage of ammonia.
For replying of carbon monoxide, acetic acid and 1-propyl alcohol, humidity has only slight influence, as available vanadium pentoxide sensor confirms.For other analyte, mensuration and the mensuration under drying condition compare under high humidity, and the loss of sensitivity is very little.When comprising the sensor array that some vanadium pentoxide sensors are formed, when being used to the smell of Analysis of Complex, this is a main advantage.
To carry out more detailed description to the present invention by embodiment and with reference to accompanying drawing now.
Fig. 1: schematically show the chemical resistance device that assembles;
Fig. 2: schematically show the arranging of 1-dimention nano particle of different types, with the space between the bridging pair of electrodes;
Fig. 3: schematically show a kind of scheme of sensor device, differentiate different analytes by the humidity that changes analyte gas;
Fig. 4: show that different sensors is for 100ppm analyte NH 3, CO and H 2Reply;
Fig. 5: show replying for 100ppm CO when having mixed the vanadium pentoxide sensor silver-colored in room temperature, in the sensor medium different level of doping;
Fig. 6: show and to have mixed vanadium pentoxide sensor (sensor 7) silver-colored in room temperature for 360ppb NH 3Reply;
Fig. 7: show and to have mixed vanadium pentoxide sensor (sensor 7) silver-colored when room temperature for NH 3The sensitivity isotherm;
Fig. 8: show vanadium pentoxide sensor (sensor 2) replying for 1ppm CO when room temperature of mixing with gold;
Fig. 9: show another kind of vanadium pentoxide sensor (sensor 3) with golden adulterant when room temperature for 20ppm H 2Reply;
Figure 10: show vanadium pentoxide chemical resistance device replying for the 30ppb butylamine when 40% relative humidity of having mixed silver-colored;
Figure 11: show vanadium pentoxide chemical resistance the replying of having mixed silver-colored for fish sample (cod);
Figure 12: show vanadium pentoxide chemical resistance replying for the 237ppm butylamine under different relative humidity of having mixed silver-colored.
Fig. 1 has schematically shown a kind of chemical resistance device, and it has the sensor medium that comprises 1-dimention nano particle (nano belt) as sensitive material.On substrate 1, be placed with mutual crossed electrode 2.Electrode structure 2 is covered by colorimetric sensor films, and this film forms 1-dimention nano particle 3.Apply constant electric current on the lead of electrode 2, the change in voltage of crossing over electrode can detect (not shown) with detecting device.
Fig. 2 is presented between the pair of electrodes 2, and the difference of 1-dimention nano particle 4 is arranged.Be single 1-dimention nano particle 4 in Fig. 2 a, bridging is on the space between the pair of electrodes 2.For the sake of simplicity, only provide a 1-dimention nano particle on the figure.Also can use some particles.In this arranging, analyte can by be adsorbed on its surface and/or by embedding the electric conductivity of modulating along the 1-dimention nano particle.Analyte also can influence electric conductivity by the conduction approach that influences between particle 4 and the electrode 2.Be presented at this arranging among Fig. 2 a, for detect those mainly by with the interaction of particle, the analyte that changes the inherent electric conductivity of one dimension particle is preferred.The 1-dimention nano particle may have more than the space between pair of electrodes wants little length.So this 1-dimention nano particle forms the netted of nano particle 4 with no sequential mode and arranges between pair of electrodes 2, shown in Fig. 2 b.That arranges among the image pattern 2a is such, and analyte can influence the inherent electric conductivity of particle and the contact resistance between particle and the electrode.In addition, analyte may change intergranular contact.In this arranging, the electricity that analyte may be promoted or reduce between the particle is led.Be presented at that to have contacted when interacting between arrange analyte and the particle among Fig. 2 b be preferred.Respectively can form the space between the 1-dimention nano particle 4, it provides convenience for analyte easily arrives nano grain surface, even also be such when sensor medium is used greatly thickness.
Fig. 3 has schematically shown sensor device, and it utilizes humidity for the influence of sensor to the sensitivity of different analytes.Analyte is provided in the sample reservoir 5, wherein contain all cpds for example amine and propyl alcohol.By carrier gas stream, for example nitrogen stream, make analyte be transported to T-valve 7 through pipeline 6 from reservoir 5.T-valve 7 is to lead to pipeline 6a in the first step, and 6b closes.The air communication that contains analyte is crossed humidity conditioner 8 and is adjusted to predetermined humidity.The humidity of air-flow is monitored by humidity detection unit 9.The air communication of humidifying is crossed further T-valve 10 and is imported into transducer room 11 then, detects first signal by sensor 12 there.Sensor 12 is connected to (not shown) on the computing machine, and it is to store and more detected signal as the effect of pick-up unit.Pipeline 6b is closed by further T-valve, does not therefore have gas to be imported into pipeline 6b.T-valve 7 and 10 is changed like this in second step, pipeline 6a is closed and pipeline 6b is opened.The air-flow that comprises analyte now will be introduced into drying unit 13, and by for example drying agent drying.Then the air-flow of drying is introduced transducer room 11, so sensor 12 detects second signal.Humidity has only very little influence for the sensitivity of 12 pairs of propyl alcohol of sensor and has a significant impact for the sensitivity of 12 pairs of amines of sensor, and in this case, relatively first and second signals promptly can be distinguished these compounds.If propyl alcohol is also had clearly intensity difference between twice signal, in the time of as under situation, seeing, just almost they cannot have been distinguished to amine.
A) the vanadium pentoxide nano belt of preparation undoped agent
The front by the wet chemistry methods of people such as J.Muster description, is used to prepare the V of undoped in above-mentioned quoted passage 2O 5The material stock of nanofiber.V 2O 5Colloidal sol is to be prepared in 40 ml waters by 0.2 gram (partially) ammonium vanadate (Aldrich reagent company) and 2 gram acid-exchange resins (Dowex 50WX8100, Aldrich reagent company).Can be observed the formation of orange colloidal sol after a few hours, the blackening of this colloidal sol along with the time.The V of length number micron 2O 5Fiber can be observed after about 3 days.This fiber in being applied to test has been placed the number time.
B) preparation of the vanadium pentoxide nano belt of silver-doped
The vanadium pentoxide nanofiber of silver-doped by above-mentioned a) described in method prepare, but at V 2O 5In solution, added silver salt (silver nitrate) in the preparation process of colloidal sol.
The vanadium pentoxide nanofiber of silver-doped is used to prepare sensor 7.
C) manufacturing of sensor
The 1-dimention nano particle is deposited on the BK7 glass substrate, and the latter is supporting the cross one another electrode structure that litho is made.Electrode structure comprises the titanium bonding coat of 5 nanometer thickness, is deposited on the gold layer of 95 nanometer thickness on it.They comprise width is that 50 pairs of finger electrodes of 10 microns are right, 10 microns at interval, and staggered totally 1800 microns.The overall dimensions of electrode structure is 2 millimeters * 2 millimeters.Before the deposition colorimetric sensor films, substrate cleans with acetone, hexane and isopropyl alcohol in ultrasonic bath, and uses oxygen plasma treatment (30 watts, 0.24 millibar, 4 minutes).The substrate that cleaned be dipped into 0.1%DAS (N-[3-(trimethoxysilyl) propyl group]-ethylenediamine, Aldrich reagent company) in the solution in water two minutes, then with the thorough rinsing of pure water and dry in airflow.This experimental implementation makes glass substrate by amino institute functionalization, the linking group when amino can be used as follow-up nanofiber deposition.The fiber that obtains in the step a) in front, by substrate at fiber at H 2Dipping is 20 seconds in the dilute suspension among the O, and dip-coating is to substrate.Substrate is used the pure water rinsing and is dry in airflow.Obtained unadulterated V in this way 2O 5Nanofiber sensor (sensor 8).
D) manufacturing of the sensor of silver-doped (sensor 7)
At c) in the manufacturing operation program described be repeated, but use b) in the vanadium pentoxide nanofiber of the silver-doped that obtains as the 1-dimention nano particle.So just obtained being called the V of the silver-doped of sensor 7 2O 5The nanofiber sensor.
E) carry out the doping of sensor by dipping
C) sensor that obtains in is immersed in the dopant solution that describes in detail in the table 1.Behind the dipping, sensor is with the thorough rinsing of pure water and dry in airflow.
Table 1: by the sensor of dipping acquisition in dopant solution
Sensor Adulterant Concentration of dopant Solvent Exposure duration
1 Silver acetate 1mg in 1ml H 2O 10 seconds
2 AuS(CH 3) 2 +Cl - 1mg in 1ml NMF 20 minutes
4 AuCl 3 1mg in 1ml NMF 30 minutes
5 Silver acetate 0.1mg in 1ml H 2O 10 seconds
6 Silver acetate 10mg in 1ml H 2O 10 seconds
F) carry out the doping (sensor 3) of sensor by evaporated metal
C) in evaporate the gold layer of last 2 nano thickness on the unadulterated sensor that obtains, obtain sensor 3.Atomic force microscopy shows the particle that has formed almost spherical.
G) sensor is to the sensitivity of gas with various
For carrying out the experiment of test gas aspect, at c)-f) described in the sensor of method preparation, be put into about 1.23 centimetres of volume 3The teflon cell made of this country in.The preparation of test gas is by a German Ober- The mass flow system made of MCZ Umwelttechnik GmbH, with carrier gas (the dry N of right quantity 2) dilution analysis thing material stock [10% analyte (H 2, CO, NH 3) at dry N 2In] and obtain required analyte concentration.Mass rate in the test cell is adjusted to 400 ml/min, and all experiments are kept constant.All experiment things carry out in room temperature.
Electrical resistance monitoring is to apply the dc electric current also with one 2002 type multimeter (Keithley company) recording voltage with a SMU 236 (Keithley company).Be exposed to the relative variation of measuring resistance after 120 seconds in the interested gas at sensor.
Table 2: sensor 1-4 replys Δ R/R to gas with various Initially
100ppm NH 3 100ppm CO 100ppm H 2
Sensor 1 +18％ +1.2％ +0.4％
Sensor 2 -17％ -6％ -0.7％
Sensor 3 -9％ -1.2％ -0.8％
Sensor 4 +13％ +1.6％ +0.2％
Replying also of sensor 1-3 is illustrated among Fig. 3.Though sensor 1 and 2 has roughly the same sensitivity (in absolute value) for ammonia, the sensitivity ratio sensor 1 of 2 couples of CO of sensor will exceed about 5 times.Just can distinguish NH by being used in combination these two kinds of sensors 3And CO.The sensitivity of 3 pairs of ammonias of sensor will be lower than sensor 1 and 2, but it is to H 2Gas is sensitiveer.This just makes this sensor occasion that is used for needs detection hydrogen preferably.
H) influence of doped level
Vanadium pentoxide sensor 1,5 and 6 with silver-doped of low-doped level (sensor 5), medium-doped level (sensor 1) and highly doped level (sensor 6) is exposed among the 100ppm CO.Replying of sensor is shown among Fig. 5.Sensor 5 shows replys and the variation of-1.3% relative resistance rate fast, the sensor 1 and 6 with medium and highly doped level then demonstrates respectively+1.0% with+1.3% relative resistance rate Δ R/R InitiallyVariation.This confirms that replying of sensor can be by changing the doped level modification.
I) the vanadium pentoxide sensor of silver-doped is to NH 3 Sensitivity
Sensor 7 is exposed in the ammonia of 360ppb.Replying of sensor is shown among Fig. 6.Sensor demonstrated fast in 120 seconds and replys, and made Δ R/R InitiallyValue reaches-1.6%.This confirms that sensor also is responsive for the very low ammonia of concentration, can provide the convalescence of replying fast and lacking.Replying that higher ammonia concentration lower sensor obtains to increase, can obviously find out in the sensitivity isotherm figure as shown in Figure 7 like that.
K) to the sensitivity of carbon monoxide
In room temperature the sensor 2 of the gold that mixes is exposed in the 1ppm CO gas.Replying of sensor is shown among Fig. 8.Even when low concentration, also can in 120 seconds, obtain Δ R/R InitiallyBe-1.7% reply.
L) to the sensitivity of hydrogen
The sensor 3 of the gold that mixes, be exposed to 20ppm H in room temperature 2In the gas.Replying of sensor is shown among Fig. 9.What obtained in 120 seconds replys Δ R/R InitiallyValue is for-0.4%.
Based on the sensor of vanadium pentoxide, can be used suitable NH 3, CO and H 2Single-sensor.Because the cross sensitivity and the different sensors of gas with various had different sensitivity, have different dopant based on V 2O 5Sensor array can be used as the sensor array of Electronic Nose.
M) under high humidity for the sensitivity of butylamine
Under 40% relative humidity condition, the sensor 7 of silver-doped is exposed in the butylamine gas of 30ppb.Replying of sensor is presented among Figure 10.Arrow indication upwards begins to use the time that contains butylamine gas, the time that downward arrow indication butylamine begins to be removed from gas phase.What obtained in 500 seconds replys Δ R/R InitiallyValue is for+1.9%.
N) detection of the amine of biogenetic derivation
Article two, fresh fish (cod) sample is produced respectively and is stored in the glass container.The gas of headroom is sampled with a micropump, and analyzes for 10 seconds by respectively they being exposed in the sensor 7 of silver-doped.Elder generation's analytical sample 1, then analytical sample 2.The dotted line that is presented among Figure 11 is the figure of noting in a day when sample is fresh.Two samples provide similar signal.Then sample 1 was stored in the refrigerator 24 hours, and sample 2 is stored at ambient temperature.Analyze this two samples in second day once more, be presented at the figure that solid line among Figure 11 is noted after corresponding to sample storage.Provide bigger the replying of signal at the signal of the sample 2 of room temperature storage than the sample 1 that in refrigerator, stores.Known most marine fishes produce amine in decomposable process.The enhancing that we can indicate sample 2 signals is to cause the faster decomposition of fish because storage temperature raises, and the result produces due to the higher levels of amine.
O) humidity is to the influence of transducer sensitivity
Sensor 7 silver-doped under the different humidity condition is exposed in the butylamine of 237ppm.In relative humidity is 5,20,30,40, and survey sensor replys under 50 and 60% the relative humidity.Replying of sensor is presented among Figure 12.The direction of arrow is the direction that indication humidity increases.Under 60% damp condition, obtain the sensitivity of highest level.

Claims (32)

1. the chemical sensitisation apparatus comprises a kind of substrate, a kind of sensor medium that on substrate, forms, and this sensor medium comprises the 1-dimention nano particle, and wherein this 1-dimention nano particle mainly is by semiconductor A xB yThe type compound is formed, wherein semiconductor A xB yCompound is vanadium pentoxide V 2O 5The device that the physics of detecting sensor medium and/or chemical property change; And provide a kind of device of controlled humidity, by this device humidifying analyte sample and be adjusted to predetermined humidity.
2. the chemical sensitisation apparatus of claim 1,1-dimention nano particle wherein is the form of nanotube, nanofiber or nano belt.
3. claim 1 or 2 chemical sensitisation apparatus, 1-dimention nano particle wherein is filling.
4. claim 1 or 2 chemical sensitisation apparatus, 1-dimention nano particle wherein has a rectangular cross section.
5. claim 1 or 2 chemical sensitisation apparatus, 1-dimention nano particle wherein provides with the pencil form.
6. claim 1 or 2 chemical sensitisation apparatus wherein further contain adulterant in the 1-dimention nano particle.
7. the chemical sensitisation apparatus of claim 6, adulterant wherein is a kind of organic compound.
8. the chemical sensitisation apparatus of claim 7, wherein this organic compound are derivant, pyrroles and the pyrroles's of the derivant, thiophene and the thiophene that are selected from mercaptan, carboxylic acid, amine, phosphine, phosphine oxide, pyridine and pyridine derivants.
9. the chemical sensitisation apparatus of claim 6, adulterant wherein is a kind of ion or ionic complex.
10. the chemical sensitisation apparatus of claim 6, adulterant wherein is added in the 1-dimention nano particle by embedding and/or is attracted on the surface of 1-dimention nano particle.
11. the chemical sensitisation apparatus of claim 1 or 2, sensor medium wherein also contain second kind of nano particle different with the 1-dimention nano particle in addition.
12. the chemical sensor of claim 11, wherein second kind of nano particle has the shape of almost spherical.
13. the chemical sensitisation apparatus of claim 11, wherein second kind of nano particle is made up of metal on substantially.
14. the chemical sensitisation apparatus of claim 1 or 2, wherein sensor device is assembled into the chemical resistance device, chemical-sensitive diode, multiterminal device, chemical-sensitive transistor, mass-sensitive device, or a kind of optical devices.
15. the chemical sensitisation apparatus of claim 1 or 2 wherein provides well heater in the position that is closely related with sensor.
16. the chemical sensitisation apparatus of claim 1 or 2 comprises at least a said 1-dimention nano particle in the sensor medium wherein, latter's bridging is on the space between two electrodes that are provided on the substrate.
17. the chemical sensitisation apparatus of claim 1 or 2 wherein provides a kind of unit of monitoring humidity on the position that is closely related with sensor medium.
18. the method for the chemical sensitisation apparatus that one of forms in the middle of the claim 1 to 17, it comprises following each step:
A) provide substrate with substrate surface;
B) provide basically by the semiconductor A that defines in the claim 1 xB yThe 1-dimention nano particle that compound is formed;
C) thus obtain sensor medium with 1-dimention nano particle coated substrate surface;
D) provide the pick-up unit of detecting sensor medium change in physical,
Wherein with of the sensitivity of analyte sample humidifying with the increase that is provided for detecting described analyte.
19. the method for claim 18,1-dimention nano particle wherein is to be arranged on the substrate surface.
20. the method for claim 18 or 19,1-dimention nano particle wherein is to be fixed on the substrate surface by the difunctional part, and this part is connected with substrate by first functional group, is connected with the 1-dimention nano particle surface by second functional group.
21. the method for claim 18 or 19 wherein in the position that is closely related with sensor medium, provides a kind of humidity conditioner and/or moisture measurement unit.
22. the method for analyte in the test samples, wherein provide comprise sensor medium and pick-up unit claim 1 to 17 in the middle of one of the chemical sensitisation apparatus, a kind of analyte is applied on the sensor medium, and the variation of this sensor medium physical property is measured by pick-up unit.
23. the method for claim 22, wherein analyte is provided in gas phase.
24. the method for claim 22 or 23, analyte wherein are a kind of amine.
25. the method for claim 22 or 23, the wherein variation of sensor medium physical property, be lower than under 100 ℃ the temperature conditions determined.
26. the method for claim 22 or 23, the wherein variation of sensor medium physical property is in the atmosphere on sensor medium, and is determined under greater than 5% condition in relative humidity.
27. the method for claim 26, wherein in the process of determination sensor medium change in physical, relative humidity remains on constant numerical value.
28. the method for claim 22 or 23, wherein sensor medium is by the water vapo(u)rous.
29. the method for claim 22 or 23, wherein finish operation for the first time earlier, wherein in analyte, regulate relative humidity and make the first kind of level that reach, then this analyte is applied on the sensor medium to obtain first numerical value of sensor medium change in physical; Finish operation for the second time again, wherein in analyte, regulate humidity to the second kind of level, then analyte is applied on the sensor medium, to obtain second numerical value of sensor medium change in physical, first and second measured value are compared, to identify analyte.
30. the method for claim 29, wherein for the first time and for the second time differing of relative humidity level is at least 10% relative humidity.
31. the method for claim 22 or 23, the wherein variation of sensor medium physical property, be lower than under 50 ℃ the temperature conditions determined.
32. the method for claim 22 or 23, the wherein variation of sensor medium physical property is determined under the temperature conditions of room temperature.
CN02827556XA 2001-11-26 2002-11-26 The use of 1d semiconductor materials as chemical sensing materials, production and operation close to room temperature Expired - Fee Related CN1618014B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP01128064.1 2001-11-26
EP01128064 2001-11-26
PCT/EP2002/013309 WO2003046536A1 (en) 2001-11-26 2002-11-26 The use of 1d semiconductor materials as chemical sensing materials, produced and operated close to room temperature

Publications (2)

Publication Number Publication Date
CN1618014A CN1618014A (en) 2005-05-18
CN1618014B true CN1618014B (en) 2010-04-28

Family

ID=8179352

Family Applications (1)

Application Number Title Priority Date Filing Date
CN02827556XA Expired - Fee Related CN1618014B (en) 2001-11-26 2002-11-26 The use of 1d semiconductor materials as chemical sensing materials, production and operation close to room temperature

Country Status (8)

Country Link
US (1) US20050072213A1 (en)
EP (1) EP1456634A1 (en)
JP (1) JP4435569B2 (en)
KR (1) KR20040054801A (en)
CN (1) CN1618014B (en)
AU (1) AU2002354154B2 (en)
CA (1) CA2468251A1 (en)
WO (1) WO2003046536A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102951603A (en) * 2011-08-19 2013-03-06 新加坡科技研究局 Methods to form substrates for optical sensing by surface enhanced raman spectroscopy (sers) and substrates formed by methods

Families Citing this family (106)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7301199B2 (en) * 2000-08-22 2007-11-27 President And Fellows Of Harvard College Nanoscale wires and related devices
US20060175601A1 (en) * 2000-08-22 2006-08-10 President And Fellows Of Harvard College Nanoscale wires and related devices
EP2298968A3 (en) * 2000-08-22 2011-10-05 President and Fellows of Harvard College Method for growing nanowires
AU2002229046B2 (en) 2000-12-11 2006-05-18 President And Fellows Of Harvard College Nanosensors
US8154093B2 (en) 2002-01-16 2012-04-10 Nanomix, Inc. Nano-electronic sensors for chemical and biological analytes, including capacitance and bio-membrane devices
US6905655B2 (en) * 2002-03-15 2005-06-14 Nanomix, Inc. Modification of selectivity for sensing for nanostructure device arrays
US7522040B2 (en) 2004-04-20 2009-04-21 Nanomix, Inc. Remotely communicating, battery-powered nanostructure sensor devices
US7547931B2 (en) 2003-09-05 2009-06-16 Nanomix, Inc. Nanoelectronic capnometer adaptor including a nanoelectric sensor selectively sensitive to at least one gaseous constituent of exhaled breath
US7948041B2 (en) * 2005-05-19 2011-05-24 Nanomix, Inc. Sensor having a thin-film inhibition layer
US7237429B2 (en) * 2002-08-30 2007-07-03 Nano-Proprietary, Inc. Continuous-range hydrogen sensors
US6849911B2 (en) 2002-08-30 2005-02-01 Nano-Proprietary, Inc. Formation of metal nanowires for use as variable-range hydrogen sensors
US7287412B2 (en) * 2003-06-03 2007-10-30 Nano-Proprietary, Inc. Method and apparatus for sensing hydrogen gas
US20070114573A1 (en) * 2002-09-04 2007-05-24 Tzong-Ru Han Sensor device with heated nanostructure
US20060263255A1 (en) * 2002-09-04 2006-11-23 Tzong-Ru Han Nanoelectronic sensor system and hydrogen-sensitive functionalization
JP3890413B2 (en) * 2003-03-12 2007-03-07 独立行政法人産業技術総合研究所 Gas sensor and manufacturing method thereof
US20070240491A1 (en) * 2003-06-03 2007-10-18 Nano-Proprietary, Inc. Hydrogen Sensor
US20050036905A1 (en) * 2003-08-12 2005-02-17 Matsushita Electric Works, Ltd. Defect controlled nanotube sensor and method of production
WO2005094221A2 (en) * 2003-09-18 2005-10-13 Nanomix, Inc. Nanostructures with electrodeposited nanoparticles
US7679563B2 (en) * 2004-01-14 2010-03-16 The Penn State Research Foundation Reconfigurable frequency selective surfaces for remote sensing of chemical and biological agents
JP3810411B2 (en) * 2004-01-23 2006-08-16 Ｎｅｃエレクトロニクス株式会社 Integrated circuit device
JP4541717B2 (en) * 2004-02-09 2010-09-08 ルネサスエレクトロニクス株式会社 Integrated circuit device and manufacturing method thereof
US20090227107A9 (en) * 2004-02-13 2009-09-10 President And Fellows Of Havard College Nanostructures Containing Metal Semiconductor Compounds
US8052932B2 (en) 2006-12-22 2011-11-08 Research Triangle Institute Polymer nanofiber-based electronic nose
JP4691687B2 (en) * 2004-05-11 2011-06-01 独立行政法人産業技術総合研究所 Organic-inorganic hybrid gas sensor material and manufacturing method thereof
JP4691688B2 (en) * 2004-05-11 2011-06-01 独立行政法人産業技術総合研究所 Organic inorganic hybrid thin film sensor
WO2006107312A1 (en) * 2004-06-15 2006-10-12 President And Fellows Of Harvard College Nanosensors
US20060102494A1 (en) * 2004-11-17 2006-05-18 Industrial Technology Research Institute Gas sensor with nanowires of zinc oxide or indium/zinc mixed oxides and method of detecting NOx gas
JP2008523590A (en) * 2004-12-06 2008-07-03 プレジデント・アンド・フェロウズ・オブ・ハーバード・カレッジ Nanoscale wire-based data storage device
WO2006070670A1 (en) * 2004-12-28 2006-07-06 Matsushita Electric Industrial Co., Ltd. Semiconductor nano-wire, and semiconductor device provided with that nano-wire
KR100604229B1 (en) * 2004-12-29 2006-07-28 학교법인고려중앙학원 Fabrication method of gas sensors by using networked GaN nanowires
TWI281539B (en) * 2005-05-11 2007-05-21 Ind Tech Res Inst Gas sensor with nanowires of zinc oxide or indium/zinc mixed oxides and method of detecting NOx gas
EP1883815A4 (en) * 2005-05-20 2008-10-22 Univ Rmit Assay device
US20100227382A1 (en) * 2005-05-25 2010-09-09 President And Fellows Of Harvard College Nanoscale sensors
WO2006132659A2 (en) * 2005-06-06 2006-12-14 President And Fellows Of Harvard College Nanowire heterostructures
TW200712486A (en) * 2005-08-03 2007-04-01 Nano Proprietary Inc Continuous range hydrogen sensor
GB0516401D0 (en) 2005-08-09 2005-09-14 Univ Cambridge Tech Nanorod field-effect transistors
KR100727413B1 (en) * 2005-08-26 2007-06-13 경북대학교 산학협력단 Process for the preparation of nir q-dot coated with bio compatable polymer for medical molecular imaging
US8510056B2 (en) * 2005-10-24 2013-08-13 Western Michigan University Research Foundation Method and integrated microsystem for detecting biomolecules in liquid
EP1790977A1 (en) * 2005-11-23 2007-05-30 SONY DEUTSCHLAND GmbH Nanoparticle/nanofiber based chemical sensor, arrays of such sensors, uses and method of fabrication thereof, and method of detecting an analyte
US20070145356A1 (en) * 2005-12-22 2007-06-28 Amlani Islamshah S Carbon nanotube interdigitated sensor
KR100812357B1 (en) * 2005-12-23 2008-03-11 한국과학기술연구원 Ultra-sensitive metal oxide gas sensor and fbrication method thereof
DE102006014713B3 (en) * 2006-03-30 2007-11-15 Drägerwerk AG Electrochemical gas sensor
US9267220B2 (en) * 2006-03-31 2016-02-23 Cornell University Nanofibers, nanotubes and nanofiber mats comprising crystaline metal oxides and methods of making the same
US8512641B2 (en) * 2006-04-11 2013-08-20 Applied Nanotech Holdings, Inc. Modulation of step function phenomena by varying nanoparticle size
JP2009540333A (en) 2006-06-12 2009-11-19 プレジデント アンド フェロウズ オブ ハーバード カレッジ Nanosensors and related technologies
KR100863764B1 (en) * 2006-07-07 2008-10-16 한국기계연구원 Flow detecting method using physical change of nano material
JP2010500559A (en) * 2006-08-11 2010-01-07 エージェンシー フォー サイエンス，テクノロジー アンド リサーチ Nanowire sensor, nanowire sensor array, and method of forming the sensor and sensor array
JP2008057998A (en) * 2006-08-29 2008-03-13 Kri Inc Nondestructive detection method of bacterial contamination in container package
JP2008083041A (en) * 2006-08-30 2008-04-10 Kri Inc Detecting element, manufacturing method therefor, and detector
WO2008033303A2 (en) 2006-09-11 2008-03-20 President And Fellows Of Harvard College Branched nanoscale wires
US20080101994A1 (en) * 2006-10-28 2008-05-01 Shabnam Virji Polyaniline Nanofiber Hydrogen Sensors
JP5009993B2 (en) 2006-11-09 2012-08-29 ナノシス・インク． Nanowire arrangement method and deposition method
WO2008127314A1 (en) 2006-11-22 2008-10-23 President And Fellows Of Harvard College High-sensitivity nanoscale wire sensors
US20100097048A1 (en) * 2007-01-04 2010-04-22 Werner Douglas H Passive detection of analytes
JP2008209249A (en) * 2007-02-27 2008-09-11 National Institutes Of Natural Sciences Oxygen gas detection element, and nanowire for oxygen gas detection element
JP4875517B2 (en) * 2007-03-05 2012-02-15 シャープ株式会社 Chemical substance sensing element, chemical substance sensing device, and method of manufacturing chemical substance sensing element
US20080236251A1 (en) * 2007-03-28 2008-10-02 Tepper Gary C Chemical Sensing Apparatuses, Methods and Systems
DE602007001133D1 (en) * 2007-03-30 2009-06-25 Sony Deutschland Gmbh Method for changing the sensitivity and / or selectivity of a chemical resistance sensor array
JP4953306B2 (en) * 2007-06-27 2012-06-13 国立大学法人九州大学 Hydrogen gas sensor manufacturing method
WO2009045473A2 (en) * 2007-10-02 2009-04-09 President And Fellows Of Harvard College Carbon nanotube synthesis for nanopore devices
US20090101501A1 (en) * 2007-10-17 2009-04-23 Tao Xiao-Ming Room temperature gas sensors
EP2068142A1 (en) * 2007-12-04 2009-06-10 Sony Corporation Use of a nanoparticle film having metal ions incorporated
EP2067525A1 (en) * 2007-12-04 2009-06-10 Sony Corporation A method of preparing a nanoparticle film having metal ions incorporated
US7827852B2 (en) * 2007-12-20 2010-11-09 General Electric Company Gas sensor and method of making
US9164073B1 (en) * 2008-02-11 2015-10-20 Pavel Nosovitskiy Multi-functional, discrete determination of concentrations of gases in a gaseous mixture
FR2937978A1 (en) * 2008-11-05 2010-05-07 Centre Nat Rech Scient Material, useful as an active material in an electrode, and for the vibrational or chemical characterization of nanoscale object in Raman spectroscopy, comprises metallic silver and vanadium
KR101201896B1 (en) * 2008-12-03 2012-11-16 한국전자통신연구원 Capacitive Type Gas Sensors and Method for Fabricating the Same
US7816681B2 (en) * 2008-12-03 2010-10-19 Electronics And Telecommunications Research Institute Capacitive gas sensor and method of fabricating the same
KR101201897B1 (en) * 2008-12-12 2012-11-16 한국전자통신연구원 Ultra High Sensitive Gas Sensors Using Semiconductor Oxide Nanofiber and Method for Preparing the Same
CN101592626B (en) * 2009-03-19 2013-03-06 中国科学院苏州纳米技术与纳米仿生研究所 Quasi-one-dimensional metal oxide nano-material biosensor and method for manufacturing same
KR100946598B1 (en) * 2009-04-24 2010-03-09 주식회사 엘파니 Solid dopants for conductive polymers, method and apparatus for preparing the same using plasma treatment, and solid doping method of conductive polymers
WO2010138506A1 (en) 2009-05-26 2010-12-02 Nanosys, Inc. Methods and systems for electric field deposition of nanowires and other devices
DE112010001858B4 (en) 2009-05-29 2013-12-24 Hach Company Chrome-free display for chloride detection
US8993346B2 (en) 2009-08-07 2015-03-31 Nanomix, Inc. Magnetic carbon nanotube based biodetection
WO2011038228A1 (en) 2009-09-24 2011-03-31 President And Fellows Of Harvard College Bent nanowires and related probing of species
KR101283685B1 (en) * 2009-11-23 2013-07-08 한국전자통신연구원 Environment Gas Sensor and Method for Preparing the Same
US20110138882A1 (en) * 2009-12-11 2011-06-16 Electronics And Telecommunications Research Institute Semiconductor gas sensor having low power consumption
JP5625172B2 (en) * 2009-12-28 2014-11-19 東亞合成株式会社 Vanadium dioxide fine particles, production method thereof, and thermochromic film
JP5419767B2 (en) * 2010-03-24 2014-02-19 オリンパス株式会社 Detection sensor, substance detection method
EP2691777A1 (en) * 2011-03-28 2014-02-05 Flir Systems, Inc. Detection of analytes including drugs
EP2773941A1 (en) * 2011-11-04 2014-09-10 Danmarks Tekniske Universitet Resonant fiber based aerosol particle sensor and method
JP6035087B2 (en) * 2012-09-06 2016-11-30 セイコーインスツル株式会社 Gas sensor, gas measuring device, and gas sensor manufacturing method
US10278617B1 (en) * 2013-03-15 2019-05-07 Invoy Holdings, Llc Method and apparatus for sensing ammonia in breath
US9896772B2 (en) 2014-03-13 2018-02-20 Innosense Llc Modular chemiresistive sensor
KR101662890B1 (en) * 2014-07-29 2016-10-06 서울대학교산학협력단 Gas sensor operable at room temperature and preparation method thereof
EP3201627B1 (en) * 2014-10-03 2020-02-12 Rite Taste, LLC System for detecting gluten in food samples
US10782285B2 (en) 2014-10-03 2020-09-22 Rite Taste, LLC Device and method for chemical analysis
KR101704122B1 (en) * 2014-10-08 2017-02-07 현대자동차주식회사 Hydrogen detecting coloration sensor
EP3286559B1 (en) 2015-04-20 2019-09-04 Tubitak The use of piezoelectric transducers modified with metal oxide-based thin films for direct detection of amine derivatives in liquid media
CN105223238A (en) * 2015-10-23 2016-01-06 中国石油大学(华东) A kind of based on Pd/SnO 2electric resistance moisture sensor of/Si heterojunction and preparation method thereof
WO2017085796A1 (en) * 2015-11-17 2017-05-26 株式会社アロマビット Odor sensor and odor measurement system
US10178963B1 (en) * 2016-06-09 2019-01-15 Dynosense, Corp. Gas collection apparatus and method to analyze a human breath sample
AT519716B1 (en) * 2017-03-14 2019-01-15 Mat Center Leoben Forschung Gmbh Particle sensor and method for measuring particle concentrations
CN107228885B (en) * 2017-06-29 2020-06-26 江苏大学 Preparation method of pigment nano vesicle bionic gas sensor
US11209416B2 (en) 2017-07-28 2021-12-28 Graphene-Dx, Inc. Device and method for chemical analysis
US11331019B2 (en) 2017-08-07 2022-05-17 The Research Foundation For The State University Of New York Nanoparticle sensor having a nanofibrous membrane scaffold
US11149318B2 (en) 2018-01-29 2021-10-19 Graphene-Dx, Inc. Methods and devices for detection of pathogens
US10942157B2 (en) * 2018-02-21 2021-03-09 Stmicroelectronics Pte Ltd Gas sensor device for detecting gases with large molecules
RU2677093C1 (en) * 2018-04-02 2019-01-15 Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) Method of manufacturing a chemoresistor based on cobalt oxide nanostructures by electrochemical method
WO2020010293A1 (en) 2018-07-06 2020-01-09 Qorvo Us, Inc. Bulk acoustic wave resonator with increased dynamic range
CN108918604A (en) * 2018-08-01 2018-11-30 济南大学 For detecting the organic-inorganic blended micrometer material and gas sensor of trimethylamine
US11788981B2 (en) * 2019-03-11 2023-10-17 Carrier Corporation Sensor for detecting gas analyte
US11879862B2 (en) * 2020-04-22 2024-01-23 Carrier Corporation Sensor for detecting gas analyte
CN112858406B (en) * 2021-01-14 2022-08-26 青岛科技大学 Method for detecting p-aminophenol by photo-induced electrochemistry
CN113640169A (en) * 2021-06-23 2021-11-12 南方医科大学皮肤病医院（广东省皮肤病医院、广东省皮肤性病防治中心、中国麻风防治研究中心） WO based on doped Sb3Nanocrystalline QCM sensor and application thereof in monitoring of respiration and skin wound humidity
CN114062443B (en) * 2021-11-10 2023-10-03 北京印刷学院 Flexible sensor for monitoring humidity of package headspace

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998026871A1 (en) * 1996-12-18 1998-06-25 Eidgenössische Technische Hochschule Zürich Nanotubes, use and manufacture of same
US5801297A (en) * 1993-09-17 1998-09-01 Alpha M.O.S. Methods and devices for the detection of odorous substances and applications
WO2001044796A1 (en) * 1999-12-15 2001-06-21 Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube devices

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6344271B1 (en) * 1998-11-06 2002-02-05 Nanoenergy Corporation Materials and products using nanostructured non-stoichiometric substances
JP3976403B2 (en) * 1998-06-10 2007-09-19 新コスモス電機株式会社 Sensor array for odor identification
WO2000029829A1 (en) * 1998-11-16 2000-05-25 California Institute Of Technology Simultaneous determination of equilibrium and kinetic properties
JP4312407B2 (en) * 1999-12-10 2009-08-12 アルザ・コーポレーション Skin treatment device for sustained transdermal drug delivery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801297A (en) * 1993-09-17 1998-09-01 Alpha M.O.S. Methods and devices for the detection of odorous substances and applications
WO1998026871A1 (en) * 1996-12-18 1998-06-25 Eidgenössische Technische Hochschule Zürich Nanotubes, use and manufacture of same
WO2001044796A1 (en) * 1999-12-15 2001-06-21 Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube devices

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Kong J et al..Nanotube Molecular Wires as Chemical Sensors.Science287 5453.2000,622,623,.
Kong J et al..Nanotube Molecular Wires as Chemical Sensors.Science287 5453.2000,622,623,. *
Muster J et al..Electrical Transport Through IndividualVanadiumPentoxideNanowires.ADVANCED MATERIALS12 6.2000,12(6),420-423.
Muster J et al..Electrical Transport Through IndividualVanadiumPentoxideNanowires.ADVANCED MATERIALS12 6.2000,12(6),420-423. *
Muster J et al..Electrical TransportThroughIndividualVanadiumPentoxideNanowires.ADVANCED MATERIALS12 6.2000,420-423.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102951603A (en) * 2011-08-19 2013-03-06 新加坡科技研究局 Methods to form substrates for optical sensing by surface enhanced raman spectroscopy (sers) and substrates formed by methods

Also Published As

Publication number Publication date
EP1456634A1 (en) 2004-09-15
JP4435569B2 (en) 2010-03-17
CA2468251A1 (en) 2003-06-05
US20050072213A1 (en) 2005-04-07
AU2002354154A1 (en) 2003-06-10
AU2002354154B2 (en) 2007-06-07
KR20040054801A (en) 2004-06-25
JP2005510711A (en) 2005-04-21
WO2003046536A1 (en) 2003-06-05
CN1618014A (en) 2005-05-18

Similar Documents

Publication Publication Date Title
CN1618014B (en) The use of 1d semiconductor materials as chemical sensing materials, production and operation close to room temperature
US7531136B2 (en) Chemical sensor
Sawan et al. Metal and metal oxide nanoparticles in the voltammetric detection of heavy metals: A review
Chirea et al. Electrochemical characterization of polyelectrolyte/gold nanoparticle multilayers self-assembled on gold electrodes
Salimi et al. Electrochemical detection of trace amount of arsenic (III) at glassy carbon electrode modified with cobalt oxide nanoparticles
Liu Towards development of chemosensors and biosensors with metal-oxide-based nanowires or nanotubes
Al-Hossainy et al. Synthesis, structural and optical properties of gold nanoparticle-graphene-selenocysteine composite bismuth ultrathin film electrode and its application to Pb (II) and Cd (II) determination
Viter et al. Metal oxide nanostructures in sensing
Zhu et al. Facile fabrication of a non-enzymatic nanocomposite of heteropolyacids and CeO2@ Pt alloy nanoparticles doped reduced graphene oxide and its application towards the simultaneous determination of xanthine and uric acid
Kundu et al. Development of electrochemical biosensor based on CNT–Fe 3 O 4 nanocomposite to determine formaldehyde adulteration in orange juice
Alizadeh et al. An innovative application of graphitic carbon nitride (g-C3N4) nano-sheets as silver ion carrier in a solid state potentiometric sensor
Patil et al. Facile synthesis of CuO nanostructures for non-enzymatic glucose sensor by modified SILAR method
Douglas et al. Silver, gold and the corresponding core shell nanoparticles: synthesis and characterization
Salagare et al. Facile synthesis of silver nanoparticle-decorated zinc oxide nanocomposite-based pencil graphite electrode for selective electrochemical determination of nitrite
Dey et al. Manganese cobalt-MOF@ carbon nanofiber-based non-enzymatic histamine sensor for the determination of food freshness
Gholivand et al. Simultaneous Determination of Trace Zinc and Cadmium by Anodic Stripping Voltammetry Using a Polymeric Film Nanoparticle Self‐Assembled Electrode
Khan Detecting inorganic arsenic below WHO threshold limit; A comparative study of various sensors
Rahman et al. Assessment of Melamine in Different Water Samples with ZnO‐doped Co3O4 Nanoparticles on a Glassy Carbon Electrode by Differential Pulse Voltammetry
Naim et al. Influence of Ag and Pd contents on the properties of PANI–Ag–Pd nanocomposite thin films and its performance as electrochemical sensor for E. coli detection
Nishan et al. Non-enzymatic colorimetric sensing of nitrite in fortified meat using functionalized drug mediated manganese dioxide
Chakraborty et al. Highly sensitive and selective electrochemical detection of lipocalin 2 by NiO nanoparticles/perovskite CeCuOx based immunosensor to diagnose renal failure
Bishnoi et al. Smart nanosensors for textiles: an introduction
Kulkarni et al. Morphological alterations in WO3-SnO2 heterostructures and their effects on chlorine sensing
Nazari et al. An electrochemical nano-sensor for determination of hydrazine using modified electrode by La 2 O 3–Co 3 O 4 nanohybrids and ionic liquid
Sharma et al. Study of electrochemical sensor and energy storage properties of MnTiO3 nano‐perovskite

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: SONY INT EUROP GMBH

Free format text: FORMER OWNER: SONY INTERNATIONAL (EUROPE) GMBH

Effective date: 20120426

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20120426

Address after: Berlin

Co-patentee after: Max-Planck-Gesellschaft zur Foerderung der Wissenschaften E.V

Patentee after: Sony Int Europ GmbH

Address before: Berlin

Co-patentee before: Max-Planck-Gesellschaft zur Foerderung der Wissenschaften E.V

Patentee before: Sony International (Europe) GmbH

C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100428

Termination date: 20131126